Suspended sediments in water bodies are classified into organic and inorganic matter and have been investigated by remote-sensing technology for years. Focusing on inorganic matter, however, detailed information such as the grain size of this matter has not been provided yet. In this study, we present a new solution for estimating inorganic suspended sediments' size distribution in highly complex Case 2 waters by using a simple spectrometer sensor rather than a backscattering sensor. An experiment was carried out in the Pearl River Estuary (PRE) in the dry season to collect the remote-sensing reflectance (Rrs) and particle size distribution (PSD) of inorganic suspended sediments. Based on Mie theory, PSDs in the PRE waters were retrieved by Rrs, colored dissolved organic matter, and phytoplankton. The retrieved median diameters in 12 stations show good agreement with those of laboratory analysis at root mean square error of 2.604 μm (27.63%), bias of 1.924 μm (20.42%), and mean absolute error of 2.298 μm (24.37%). The retrieved PSDs and previous PSDs were compared, and the features of PSDs in the PRE waters were concluded.